Integrated cluster to enable next generation interconnect

ABSTRACT

Embodiments of the present invention generally relate to methods for forming a metal structure and passivation layers. In one embodiment, metal columns are formed on a substrate. The metal columns are doped with manganese, aluminum, zirconium, or hafnium. A dielectric material is deposited over and between the metal columns and then cured to form a passivation layer on vertical surfaces of the metal columns.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit of U.S. Provisional Patent ApplicationSer. No. 61/790,352, filed Mar. 15, 2013, which is herein incorporatedby reference.

BACKGROUND

1. Field

Embodiments of the present invention generally relate to a process offorming an encapsulation layer.

2. Description of the Related Art

Integrated circuits have evolved into complex devices that can includemillions of components (e.g., transistors, capacitors and resistors) ona single chip. The evolution of chip designs continually requires fastercircuitry and greater circuit densities. The demand for greater circuitdensities necessitates a reduction in the dimensions of the integratedcircuit components.

As the dimensions of the integrated circuit components are reduced(e.g., sub-micron dimensions), the materials used to fabricate suchcomponents contribute to the electrical performance of such components.For example, low resistivity metal interconnects provide conductivepaths between the components on integrated circuits.

One method for forming vertical and horizontal interconnects is by adamascene or dual damascene method. In the damascene method, one or moredielectric materials, such as the low k dielectric materials, aredeposited and pattern etched to form the vertical interconnects, i.e.vias, and horizontal interconnects, i.e., lines. Conductive materials,such as copper containing materials, and other materials, such asbarrier layer materials used to prevent diffusion of copper containingmaterials into the surrounding low k dielectric, are then inlaid intothe etched pattern. However, due to the size induced resistivityeffects, conventional damascene process flows may soon reach a scalingimpasse.

Therefore, an improved method of forming the metal interconnects andpassivation layers to prevent metal diffusion is needed.

SUMMARY

Embodiments of the present invention generally relate to methods forforming a metal structure and passivation layers. In one embodiment,metal columns are formed on a substrate. The metal columns are dopedwith manganese, aluminum, zirconium, or hafnium. A dielectric materialis deposited over and between the metal columns and then cured to form apassivation layer on vertical surfaces of the metal columns.

In one embodiment, a method for forming passivation layers is disclosed.The method includes forming metal columns over a substrate, and eachmetal column is doped with manganese, aluminum, zirconium, or hafnium.The method further includes depositing a dielectric material between andover the metal columns, and curing the dielectric material to form apassivation layer on vertical surfaces of the metal columns.

In another embodiment, a method for forming passivation layers isdisclosed. The method includes forming metal columns over a substrate,selectively depositing a conformal layer comprising manganese, aluminum,zirconium, or hafnium on vertical surfaces of the metal columns,depositing a dielectric material between and over the metal columns andthe conformal layer, and curing the dielectric material to form apassivation layer on the vertical surfaces of the metal columns.

In another embodiment, a method for forming passivation layers isdisclosed. The method includes forming metal columns over a substrate,depositing a dielectric layer comprising silicon nitride or carbon dopedsilicon nitride over the metal columns and the substrate and on verticalsurfaces of the metal columns, depositing a dielectric material betweenand over the dielectric layer, and curing the dielectric material toform a passivation layer over and on the vertical surfaces of the metalcolumns.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the presentinvention can be understood in detail, a more particular description ofthe invention, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawings. Itis to be noted, however, that the appended drawings illustrate onlytypical embodiments of this invention and are therefore not to beconsidered limiting of its scope, for the invention may admit to otherequally effective embodiments.

FIGS. 1A-1D depict schematic cross sectional views of a patternedfeature on a substrate at different process steps according to anembodiment described herein.

FIGS. 2A-2E depict schematic cross sectional views of a patternedfeature on a substrate at different process steps according to anembodiment described herein.

FIGS. 3A-3E depict schematic cross sectional views of a patternedfeature on a substrate at different process steps according to anembodiment described herein.

To facilitate understanding, identical reference numerals have beenused, where possible, to designate identical elements that are common tothe figures. It is contemplated that elements and features of oneembodiment may be beneficially incorporated in other embodiments withoutfurther recitation.

DETAILED DESCRIPTION

Embodiments of the present invention generally relate to methods forforming a metal structure and passivation layers. In one embodiment,metal columns are formed on a substrate. The metal columns are dopedwith manganese, aluminum, zirconium, or hafnium. A dielectric materialis deposited over and between the metal columns and then cured to form apassivation layer on vertical surfaces of the metal columns.

FIGS. 1A-1D depict schematic cross sectional views of a patternedfeature 100 on a substrate at different process steps according to anembodiment described herein. As shown in FIG. 1A, a metal barrier layer104 is disposed over a layer 102. The layer 102 may be a dielectriclayer disposed over conductive contacts disposed at a lower level. Thebarrier layer 104 may include one or more barrier materials such as, forexample, tantalum, tantalum nitride, tantalum silicon nitride, titanium,titanium nitride, titanium silicon nitride, tungsten nitride, siliconnitride, ruthenium nitride, derivatives thereof, alloys thereof andcombinations thereof. The barrier layer 104 may be formed using asuitable deposition process, such as atomic layer deposition (ALD),chemical vapor deposition (CVD), physical vapor deposition (PVD) orelectroless deposition.

A conductive layer 106 is disposed over the barrier layer 104. Theconductive layer 106 may be a doped metal such as copper (Cu), cobalt(Co), or tungsten (W) doped with manganese (Mn), aluminum (Al),zirconium (Zr), or hafnium (Hf). The conductive layer 106 may be a dopedsilicide such as nickel silicide or cobalt silicide doped with Mn, Al,Zn, or Hf. In one embodiment, the conductive layer 106 is Cu doped withMn. A metal etch hard mask layer 108 is disposed over the conductivelayer 106 and a bottom anti reflecting coating (BARC) layer 110 isdisposed over the metal etch hard mask layer 108. A photoresist layer112 is disposed over the BARC layer 110. One or more reactive ionetching (RIE) processes are performed to transfer the pattern of thephotoresist layer 112 to the BARC layer 110, the metal etch hard masklayer 108, and the conductive layer 106. The remaining photoresist layer112 and the BARC layer 110 are subsequently removed, leaving metalcolumns 114 sandwiched between the metal etch hard mask layer 108 andthe barrier layer 104, as shown in FIG. 2B.

Alternatively, the metal columns 114 may be formed with a sacrificiallayer. The sacrificial layer, such as silicon oxide, may be depositedover the layer 102 before the deposition of the conductive layer 106.Trenches are formed in the sacrificial layer and the conductive layer106 and barrier layer 104 are deposited into the trenches. Thesacrificial layer is subsequently removed, forming the metal columns114.

After the formation of the metal columns 114, a degas and pre-cleanprocess is performed to remove any moisture and to reduce any metaloxide. The pre-clean process may be varied ranging from H₂ anneal to H₂or NH₃ plasmas or derivatives of the same. In an integrated fashion(under vacuum), the substrate is moved to a process chamber, where aflowable low k dielectric film 120 is deposited over and between themetal columns 114, the metal etch hard mask layer 108 and the barrierlayer 104, as shown in FIG. 1C. The low k dielectric film 120 mayinclude carbon-containing silicon oxides (SiOC), such as BLACK DIAMOND®and BLACK DIAMOND® II available from Applied Materials, Inc., of SantaClara, Calif.

Next, the substrate may be transferred to another process chamber whileunder vacuum. The low k dielectric film 120 is cured through a thermalprocess combined with UV or e-beam as additional energy sources.Alternatively, the curing of the dielectric film 120 may be performed inthe same chamber where the low k dielectric film 120 is deposited.

The curing temperature is about 400 degrees Celsius or higher, and atthis temperature, the dopants in the metal columns 114 out diffuse tothe vertical surfaces of the metal columns 114. The dopants' outdiffusion is not only due to the thermal considerations, but also thedopants' affinity to oxygen, which is a component of the low kdielectric film 120. At the interface between the vertical surfaces ofthe metal columns 114 and the low k dielectric film 120, the dopantsreact with oxygen and silicon in the low k dielectric film 120, formingsilicate type passivation layers 122. The passivation layers 122 maycomprise manganese silicate (MnSiO_(x)), aluminum silicate (AlSiO_(x)),zirconium silicate (ZrSiO_(x)), or hafnium silicate (HfSiO_(x)). Thesilicate type passivation layers 122 may prevent metal diffusion intothe dielectric film 120, hence passivate the metal columns. Thepassivation layers 122 are self-aligned when self-formed on exposedmetal surfaces.

FIGS. 2A-2E depict schematic cross sectional views of a patternedfeature 200 on a substrate at different process steps according to anembodiment described herein. As shown in FIG. 2A, the substrate has aconductive layer 206 is disposed over a barrier layer 204 and adielectric layer 202. The conductive layer 206 may be a metal such asCu, Co, W or a silicide such as nickel silicide or cobalt silicide. Inone embodiment, the conductive layer 206 is Cu. A photoresist layer 212,a BARC layer 210, and a metal etch hard mask layer 208 are disposed overthe conductive layer 206.

One or more RIEs are performed to transfer the pattern of thephotoresist layer 212 to the conductive layer 206. As a result, metalcolumns 214 are formed, as shown in FIG. 2B. A degas and pre-cleanprocess is performed to remove any moisture and to reduce any metaloxide. The pre-clean process may be varied ranging from H₂ anneal to H₂or NH₃ plasmas or derivatives of the same. In an integrated fashion(under vacuum), the substrate is moved to a process chamber in whichconformal layers 218 are selectively deposited on the vertical surfacesof the metal columns 214. The conformal layer 218 comprises Mn, Al, Zr,or Hf. The selective deposition of the conformal layers 218 on thevertical surfaces of the metal columns 214 may be achieved by firstdeactivating the surfaces of the dielectric layer 202, the barrier layer204, and the metal etch hard mask layer 208. The deactivation may beaccomplished by any suitable method, such as reacting the surfaces to bedeactivated with alkylsilane compounds either in vapor phase or insolution. After the surfaces of the dielectric layer 202, the barrierlayer 204, and the metal etch hard mask layer 208 are deactivated, theconformal layers 218 may be deposited by CVD and the conformal layers218 would only formed on the vertical surfaces of the metal columns 214,as shown in FIG. 2C.

In an integrated fashion (under vacuum), the substrate is moved to aprocess chamber, where a flowable low k dielectric film 220 is depositedover and between the metal columns 214, the conformal layers 218, themetal etch hard mask layer 208 and the barrier layer 204, as shown inFIG. 2D. The low k dielectric film 120 may include carbon-containingsilicon oxides (SiOC), such as BLACK DIAMOND® and BLACK DIAMOND® IIavailable from Applied Materials, Inc., of Santa Clara, Calif. Thedeposition of the low k dielectric film 220 is at a low temperaturewhere the conformal layers 218 would not react with the oxygen and thesilicon in the dielectric film 220.

Next, the substrate may be transferred to another process chamber whileunder vacuum. The low k dielectric film 220 is cured through a thermalprocess combined with UV or e-beam as additional energy sources.Alternatively, the curing of the dielectric film 220 may be performed inthe same chamber where the low k dielectric film 220 is deposited.

The curing temperature is about 400 degrees Celsius or higher, and atthis temperature, conformal layers 218 react with oxygen and silicon inthe low k dielectric film 220, forming silicate type passivation layers222. The passivation layers 222 may comprise manganese silicate(MnSiO_(x)), aluminum silicate (AlSiO_(x)), zirconium silicate(ZrSiO_(x)), or hafnium silicate (HfSiO_(x)). The silicate typepassivation layers 222 may prevent metal diffusion into the dielectricfilm 220, hence passivate the metal columns. The passivation layers 222are self-aligned when self-formed on exposed metal surfaces.

FIGS. 3A-3E depict schematic cross sectional views of a patternedfeature 300 on a substrate at different process steps according to anembodiment described herein. As shown in FIG. 3A, the substrate has aconductive layer 306 disposed over a barrier layer 304 and a dielectriclayer 302. The conductive layer 306 may be a metal such as Cu, Co, or W.The conductive layer 306 may also be a silicide such as nickel silicideor cobalt silicide. In one embodiment, the conductive layer 306 is Cu. Aphotoresist layer 312, a BARC layer 310, and a metal etch hard masklayer 308 are disposed over the conductive layer 306.

Again one or more RIEs may be performed to form metal columns 314, asshown in FIG. 3B, and a degas and pre-clean process may be performed toremove any moisture and to reduce any metal oxide.

Next, as shown in FIG. 3C, a dielectric layer 318 is conformallydeposited over the dielectric layer 302 and the metal etch hard masklayer 308, and on the sides of the metal etch hard mask layer 308, themetal columns 314, and the barrier layer 304. The dielectric layer 318may be silicon nitride (SiN), or carbon doped silicon nitride (SiCN). Ifthe dielectric layer is deposited at a high temperature in excess to 300degrees Celsius, and the thickness of the dielectric layer is betweenabout 1 to about 10 nm, the dielectric layer may have good barrierproperties. However, the dielectric layer deposited at over 300 degreesCelsius does not provide sufficient counter stress to prevent hillockingof the metal columns 314 under temperature excursion. Thus, thedielectric layer 318 may be deposited at a lower temperature, such asbetween about 50 degrees Celsius to about 200 degrees Celsius.

In one embodiment, the dielectric layer 318 is a SiCN layer and isdeposited by CVD. The silicon-containing precursors may also containcarbon for the CVD of SiCN layer. The silicon containing precursors maybe 1,3,5-trisilapentane, 1,4,7-trisilaheptane, disilacyclobutane,trisilacyclohexane, 3-methylsilane, silacyclopentene, silacyclobutane,and trimethylsiylacetylene, among others. In addition to thesilicon-containing precursor, an energized nitrogen-containingprecursor, such as ammonia, hydrazine, amines, NO, N₂O, or NO₂ may beadded to the deposition chamber. The energized nitrogen-containingprecursor may contribute some or all of the nitrogen constituent in thedeposited SiCN layer.

After the dielectric layer 318 is deposited, the substrate is moved to aprocess chamber in an integrated fashion (under vacuum), where aflowable low k dielectric film 320 is deposited over the dielectriclayer 318, as shown in FIG. 3D. The low k dielectric film 320 mayinclude carbon-containing silicon oxides (SiOC), such as BLACK DIAMOND®and BLACK DIAMOND® II available from Applied Materials, Inc., of SantaClara, Calif.

The substrate may be transferred to another process chamber while undervacuum. The low k dielectric film 320 is cured through a thermal processcombined with UV or e-beam as additional energy sources. Alternatively,the curing of the dielectric film 320 may be performed in the samechamber where the low k dielectric film 320 is deposited.

The curing temperature is about 400 degrees Celsius or higher, and atthis temperature, the silicon-hydrogen and silicon-hydroxide bonds inthe dielectric layer 318 are reduced, enhancing cross-linking anddensification. Therefore, the dielectric layer 318 now has good barrierproperties, thus becoming a passivation layer 322. Other treatments ofthe dielectric layer 318, such as by high density plasma (HDP), e-beam,microwave, or implantation, may also improve the barrier properties ofthe dielectric layer 318, thus, forming the passivation layer 322.

In summary, methods for forming passivation layers for metal columns aredisclosed. The passivation layers may be self-formed and self-alignedduring the curing process of the low k dielectric layer, as a result ofthe dopants in the metal columns moving to the interface and reactingwith the oxygen and silicon in the low k dielectric layer.

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

The invention claimed is:
 1. A method for forming passivation layers,comprising: forming metal columns over a substrate, wherein each metalcolumn has vertical surfaces and is doped with manganese, aluminum,zirconium, or hafnium; depositing a dielectric material between and overthe metal columns; and curing the dielectric material to form apassivation layer on the vertical surfaces of the metal columns.
 2. Themethod of claim 1, wherein the metal columns are formed by forming ametal layer over the substrate and performing one or more reactive ionetching processes on the metal layer.
 3. The method of claim 1, whereinthe metal columns are formed by depositing a sacrificial layer over thesubstrate, forming a plurality of trenches in the sacrificial layer,depositing a metal layer into the trenches, and removing the sacrificiallayer.
 4. The method of claim 1, wherein the dielectric material is alow k dielectric film.
 5. The method of claim 1, wherein the dielectricmaterial includes carbon-containing silicon oxides.
 6. The method ofclaim 1, further comprising a pre-clean process before depositing thedielectric material between and over the metal columns.
 7. The method ofclaim 1, wherein the metal columns comprises copper, cobalt, tungsten,nickel silicide, or cobalt silicide.
 8. The method of claim 1, whereinthe curing the dielectric material is performed by a thermal processcombined with UV or e-beam as additional energy source.
 9. The method ofclaim 1, wherein the curing the dielectric material is performed at atemperature of about 400 degrees Celsius or greater.
 10. The method ofclaim 1, wherein the passivation layer comprises manganese silicate,aluminum silicate, zirconium silicate, or hafnium silicate.
 11. Amethod, comprising: forming metal columns over a substrate, wherein eachmetal column is doped with manganese, aluminum, zirconium, or hafnium;depositing a dielectric material between and over the metal columns,wherein the dielectric material is in contact with surfaces on sides ofeach metal column; and curing the dielectric material to form apassivation layer on the surfaces of each metal column.
 12. The methodof claim 11, wherein the dielectric material comprises a low kdielectric material.
 13. The method of claim 11, wherein the dielectricmaterial comprises carbon-containing silicon oxides.
 14. The method ofclaim 11, wherein each metal column further comprises doped copper,cobalt, or tungsten.
 15. A method, comprising: forming a dielectriclayer over a substrate; forming a barrier layer on the dielectric layer;forming a conductive layer on the barrier layer, wherein the conductivelayer comprises a doped metal; removing portions of the conductive layerto form metal column; depositing a dielectric material between and overthe metal columns, wherein the dielectric material is in contact withsurfaces on sides of each metal column; and curing the dielectricmaterial to form a passivation layer on the surfaces of each metalcolumn.
 16. The method of claim 15, wherein the doped metal of theconductive layer comprises a metal doped with manganese, aluminum,zirconium, or hafnium.
 17. The method of claim 15, wherein thedielectric material comprises a low k dielectric material.
 18. Themethod of claim 17, wherein the dielectric material comprisescarbon-containing silicon oxides.